ARTICLE

pubs.acs.org/IECR

Improving the Adsorption of Heavy Metals from Water Using

Commercial Carbons Modified with Egg Shell Wastes
Alejandro Guijarro-Aldaco,† Virginia Hern
andez-Montoya,† Adrian Bonilla-Petriciolet,†,*
Miguel A. Montes-Mor
an,‡ and Didilia I. Mendoza-Castillo†
†
Instituto Tecnol
ogico de Aguascalientes, Adolfo L
opez Mat
eos 1801 Ote., Fracc. Bonagens, Aguascalientes, M
exico, 20256
‡
Instituto Nacional del Carb
on, CSIC, Apartado 73, Oviedo, Spain ES-33080

ABSTRACT: We introduce the application of hen egg shell waste to improve the adsorption capacities of heavy-metal ions using
commercial carbons via the modification of their surface chemistry. Specifically, a calcium solution extracted from egg shell waste has
been used as a low-cost activation agent to improve the adsorption properties of three commercial carbons. An orthogonal array of
the Taguchi method has been applied to identify the optimal conditions for the adsorbent modification process using the Zn2+ batch
adsorption, at 30 °C and pH 5, as the response variable. Our results show that maximum adsorption capacities of Cd2+, Ni2+, and Zn2+
ions, at 30 °C and pH 5, may increase up to 15 times, with respect to the results obtained using the commercial adsorbent without
modification. The improvement of adsorbent performance may be related to the formation of calcium phosphate on the carbon
surface. Finally, adsorption studies in binary metal solutions were performed to identify the competitive effects in multicomponent
adsorption, using calcium-modified carbons.

1. INTRODUCTION of M. oleifera. These authors showed that the adsorption capacity

Wastewaters from several industrial activities are an important
source of environmental pollution, because of their high content
of heavy-metal ions. Heavy metals are biologically important,
because of their toxicity for living organisms, including human
beings. Currently, water treatment technologies for the removal
of heavy-metal ions include chemical precipitation, membrane
filtration, ion exchange, electrochemical processes, and
adsorption.1 Adsorption is one of the most important methods
for wastewater treatment and offers several advantages for heavy-
metal removal, especially when the metal concentrations are in
the range of 1
100 ppm.
Until now, several studies have reported the application of
different adsorbents for the removal of heavy-metal ions from
aqueous solution.2
11 In particular, activated carbon (AC) has
been used for a long time to remove heavy metals from
wastewaters,4,12
16 and its performance depends on two impor-
tant factors: (1) the textural parameters and (2) the surface
functional groups.13,15 The adsorption capacities of commercial
carbons for heavy-metal ions are usually low (i.e., < 10.0 mg g
1),
since these adsorbents are produced in large scale and are
synthesized using standard procedures, which have been devel-
oped for general applications. Therefore, an additional modifica-
tion of the carbon surface chemistry is required to increase the
adsorbed amount of these toxic pollutants. To date, many carbon
surface modification methods have been introduced, including
both chemical and physical treatments.17 Specifically, chemical
treatments are commonly used for improving the adsorption of
heavy metals on carbons. For example, the modification of
carbon surface by impregnation with anionic surfactants such
as the sodium dodecyl sulfate, sodium dodecyl benzene sulfo-
nate, or dioctylsulfosuccinate sodium is suitable to improve the
removal of Cd2+ ions in aqueous solution.18 Nadeem et al.19 have
also studied the adsorption of Cd2+ ions from aqueous solution
using surfactant-modified carbons obtained from husk and pods
of carbons can be significantly enhanced by modification with
surfactants. In another study,20 the carbon modification with
tartrazine has been successfully applied to increase the adsorbed
amount of Pb2+, Cd2+, and Cr3+ ions, while the modification of
commercial coconut activated carbon using HNO3 and NaOH
for the selective adsorption of Cr6+ has been also reported.21
Recently, some authors22,23 have reported the chemical surface
modification of commercial carbons using different oxidizing
agents such as HNO3, H2O2, and Fe(NO3)3. On the other hand,
physical treatments are used to introduce specific compounds on
the carbon surface. For instance, SO2 gas can be used to
introduce sulfur groups on the carbon surface for the selective
adsorption of cadmium.24
Alternatively, both physical and chemical treatments can be
simultaneously used in the preparation or modification of
carbons, to enhance their adsorption properties. Some examples
of these studies are activated carbons obtained by carbonization
of bagasse impregnated with concentrated sulfuric acid, followed
by a treatment with carbon dioxide at 900 °C for the removal of
hexavalent chromium,25 and activated carbons obtained from
date pits using different activation methods for the removal of
lead and cadmium.26 However, a significant disadvantage of these
approaches is that the reagents used in the carbon modification
may imply a significant additional cost for the treatment process.
Therefore, the use of wastes and industrial byproduct is an
attractive alternative for developing low-cost activation reagents.
In the present study, an activation agent obtained from hen
egg shells (HES) is proposed for the chemical treatment of three
commercial carbons prepared from different precursors. HES are
Received: April 1, 2011
Accepted: June 23, 2011
Revised: June 23, 2011
Published: June 23, 2011

r 2011 American Chemical Society 9354 dx.doi.org/10.1021/ie2006627 | Ind. Eng. Chem. Res. 2011, 50, 9354–9362
Industrial & Engineering Chemistry Research
Table 1. Chemical and Physical Properties of the Commercial Carbons Used in This Study
parameter coconut shell carbon, CC
composition (%)
carbon 93.45
hydrogen 1.22
nitrogen 1.43
sulfur 0.08
oxygen 4.15
BET surface area, SBET (m2 g
1) 399
total pore volume, Vtotal (cm3 g
1) 0.172
micropore volume, Vmic (cm3 g
1) 0.160
pore diameter, Dp (nm) 1.726
widely generated from the bakery industry, homes, and restau-
rants; because of their physicochemical properties, these wastes
may have several applications in metallurgy, bioremediation, and
materials science.27 In the field of water treatment, HES wastes
also have been applied as heavy-metal sorbents;28,29 however, for
some metallic ions, the raw HES adsorption capacities are
considered low. In particular, the calcium content of HES (i.e.,
94% of calcium carbonate)30 can be used as an activation agent
for improving carbon adsorption properties. Note that this cation
is thought to play an important role in the removal of heavy
metals through ion exchange and other mechanisms. Therefore,
in this study, we introduce the application of HES wastes to
improve the adsorption of heavy-metal ions on commercial
carbons via modification of their surface chemistry. The com-
mercial carbons selected for this work have a low adsorption
capacity for heavy metals (i.e., < 1.0 mg g
1) and they have been
used as case study to illustrate the application of HES for
developing new adsorbents to remove heavy metals from waste-
waters. To identify the optimal conditions for the modification
process of the selected commercial carbons, a Taguchi orthogo-
nal array was applied, where the adsorption capacity of Zn2+ ions
at 30 °C, pH 5, and batch conditions was defined as the response
variable. In addition, the adsorption isotherms of Cd2+ and Ni2+
ions at 30 °C and pH 5 were obtained to determine the
adsorption capacity of the modified carbons in comparison with
those obtained using the raw commercial carbons. Finally,
adsorption studies in binary solutions of these metal ions were
performed to identify the competitive removal effects in multi-
component solutions of heavy metals using calcium-modified
carbons.
2. EXPERIMENTAL METHODOLOGY
2.1. Description and Characterization of Commercial Car-
bons. In this study, three types of commercial carbons provided
by Clarimex Company (Mexico) were used. For the selection of
these commercial carbons, two considerations were made: (1)
carbons must be prepared from different precursors and (2) all of
them were previously subjected to a physical activation process
(i.e., using water steam). Thus, the selected commercial adsor-
bents are coconut shell carbon (CC), bituminous carbon (BC),
and lignite carbon (LC). Table 1 provides the chemical and
physical properties of these commercial carbons. In our study,
these carbons were milled and sieved to retain the 18
20 mesh
fractions. These carbon particles were washed with deionized
9355
ARTICLE
Adsorbent
bituminous carbon, BC lignite carbon, LC
87.3 77.71
0.84 1.40
0.56 0.78
0.29 0.39
3.48 6.10
961 658
0.529 0.697
0.369 0.250
2.203 4.238
Figure 1. Experimental procedure for the surface modification of com-
mercial carbons using a calcium solution extracted from egg shell wastes.
water until pH was constant and, finally, they were dried at 70 °C
for 24 h. These samples were used to perform the modification of
carbon surface chemistry and the adsorption experiments.
With respect to the characterization of commercial adsorbents,
the content of carbon, hydrogen, nitrogen, and sulfur in the
carbons was obtained with a LECO Model CHNS-932 elemental
analyzer and the oxygen content with a LECO Model VTF-900
system. Carbon samples were heated at 815 °C under an air
atmosphere for 1 h (UNE 32004 standard) to determine their
inorganic fraction contents (i.e., ash content). The obtained
ashes were analyzed by X-ray diffraction (XRD). Diffraction
patterns were recorded in a Bruker Model D8 Advance diffract-
ometer equipped with a Cu KR X-ray source, operated at 40 kV
and 40 mA. A single G€obel mirror configuration was used to
monochromatize and focus the X-rays on the sample, attaining
highly efficient parallel beam geometry. Diffraction data were
collected by step scanning with a step size of 0.02° 2θ and a scan
step time of 5 s. Finally, the textural parameters were calculated
from the N2 adsorption isotherms at
196 °C, using a Micro-
meritics TriStar II 3020 volumetric adsorption system. Prior to
measurement, samples were outgassed overnight by heating at
523 K under vacuum. The experimental points of the nitrogen
isotherms were analyzed using suitable methods for microporous
and mesoporous materials.
dx.doi.org/10.1021/ie2006627 |Ind. Eng. Chem. Res. 2011, 50, 9354–9362
Industrial & Engineering Chemistry Research ARTICLE

Table 2. Experimental Layout Using the L9 Taguchi Orthogonal Array for the Chemical Modification of Commercial Carbons
Using Egg Shell Wastes

Factors Zn2+ Adsorbed Amount (mg g
1)

A: carbon B: acid C: concentration of D: temperature of thermal

experiment type a treatment b calcium solution (vol %) treatment (°C) label replicate 1 replicate 2

1 CC none 25 200 CC-1 0.48 0.41

2 CC HCl 50 400 CC-2 6.04 5.90
3 CC H3PO4 100 600 CC-3 10.70 10.70
4 BC none 50 600 BC-1 0.89 1.03
5 BC HCl 100 200 BC-2 1.17 1.23
6 BC H3PO4 25 400 BC-3 5.93 5.88
7 LC none 100 400 LC-1 2.40 2.40
8 LC HCl 25 600 LC-2 1.23 1.23
9 LC H3PO4 50 200 LC-3 3.84 3.64
a
CC, coconut shell carbon; BC, bituminous carbon; and LC, lignite carbon. b In this stage, we used an acid concentration of 1 M.

2.2. Modification of Surface Chemistry of Commercial
Carbons by Using Egg Shell Wastes. Commercial carbons
were modified using a calcium solution extracted from HES.
Specifically, HES wastes were washed with deionized water and
dried at 35 °C. HES particles were milled and sieved to retain the
35
40 mesh fractions. The calcium solution was obtained after
soaking these particles with acetic acid (25 vol %). This mixture
(i.e., HES and acetic acid) was shaken using a temperature-
controlled shaker operated at 150 rpm for 5 h. A ratio of 0.05 g of
HES per 1 mL of acetic acid (25 vol %) was used in this stage.
This solution was filtered to separate the membrane of HES,
because it is insoluble in acetic acid. Finally, this calcium solution
was used for the impregnation of the commercial adsorbents.
The chemical modification of commercial carbons was
performed using a three-step procedure: (1) pretreatment of
adsorbents using an acid solution, (2) calcium impregnation of
carbons using the solution extracted from HES, and (3)
thermal treatment of calcium-impregnated carbons. Figure 1
provides a schematic diagram for the different stages of this
modification process. For the acid pretreatment of the com-
mercial adsorbents, a ratio of 0.2 g of carbon per mL of acid
solution was used. This pretreatment was performed at 30 °C
for 2 h and under constant stirring (150 rpm). Later, the acid
solution was evaporated at 55 °C and, finally, carbon samples
were dried at 100 °C for 15 h. With respect to the carbon
impregnation, a ratio of 0.02 g of adsorbent per mL of calcium
solution was used. The contact time of adsorbent-impregna-
tion solution was 4 h, and all experiments were performed at
30 °C using a temperature-controller stirrer operated at
150 rpm. The solution was evaporated at 55 °C and the
calcium-impregnated carbons were dried at 110 °C for 15 h.
Finally, the impregnated carbons were heated at desired
temperature for 3 h. The modified adsorbents were washed
with deionized water at 50 °C until pH was constant and finally
dried at 100 °C for 24 h. These modified carbons were used in
the adsorption experiments.
The application of experimental designs is a robust approach
to optimize the experimental conditions for the preparation and
modification of activated carbons.5,6,31 In this study, the Taguchi
method was used to optimize the carbon surface modification
process.32,33 A L9 orthogonal array was applied in our experi-
ments (see Table 2). The selected factors were as follows: carbon
type (Factor A), acid treatment (Factor B), calcium concentration
9356
of the activation agent (Factor C), and temperature of thermal
treatment (Factor D). For all factors, we have considered three
levels in the experimental design (see Table 2). Note that the
different concentrations of activation agent (expressed as a
volume percentage) were obtained by dilution of the original
calcium solution extracted from HES. The response variable of
this experimental design was the adsorbed amount of Zn2+ ions
at 30 °C and batch conditions employing an adsorbent dosage
of 4 g L
1. It is convenient to remark that Zn2+ has been
selected as the case study, because the literature indicates that
the removal of this metal is usually difficult and traditional
commercial carbons may show a low Zn2+ adsorption
capacity.34,35 Herein, we assume that optimization of the
operating conditions of the carbon modification process, using
Zn2+ removal as the response variable, will also imply an
improvement of adsorption properties for other metallic spe-
cies not considered in our experimental design. Finally, we have
selected the adsorption capacity (expressed in units of mg g
1)
instead of the adsorption capacity normalized by the adsorbent
surface area (expressed in units of mg g
1 m
2) as the response
variable of the experimental design, because the adsorbent
surface chemistry plays a major role in the removal of heavy
metals. In the following sections, we will provide results to
support this fact.
The statistical analysis of experimental design included a
discussion of the statistical weight of each factor in the modifica-
tion process of commercial adsorbents and a variance analysis.
Calculations were performed according with the basic concepts
of the Taguchi method.32,33 In particular, Taguchi methodology
analyzes both the mean response for each run in the inner array
and the variance using a proper function for the signal-to-noise
ratio (S/N):
2 3
6
∑
ð1=Yi 2 Þ
7
S=N ¼
10 log4 i 5 ð1Þ
n
where Yi are the values of the response variable obtained in each
of the different replicates n performed under given experimental
conditions. An analysis of variance (ANOVA) was used to
perform a systematic analysis of the relative importance of each
factor, with respect to the adsorption capacity of modified
carbons using HES wastes. This analysis is based on the following
dx.doi.org/10.1021/ie2006627 |Ind. Eng. Chem. Res. 2011, 50, 9354–9362
Industrial & Engineering Chemistry Research
Figure 2. Graphs of S/N response for the chemical modification of
commercial carbons using egg shell wastes.
equations:
" #
N T2
SST ¼ ∑
i¼1
Yi2

N
ð2Þ
" !#
kF
Fi2 T2
SSF ¼ ∑
i¼1 nFi


N
ð3Þ
SSF
σF ¼ ð4Þ
vF
where T is the sum of all observations, N the total number of
observations, Fi the sum of observations under the level i, nFi the
number of observations under the level i, kF the number of levels
of factor F, SST the total sum of squares, SSF the sum of squares
for factor F, vT the total degrees of freedom (i.e., N
1), vF the
degrees of freedom of factor F (i.e., kF
1), and σF is the variance
for factor F, respectively.
2.3. Adsorption Experiments. 2.3.1. Taguchi Design. For the
Taguchi experimental design, batch sorption experiments were
performed using Zn2+ solutions with an initial concentration of
100 mg L
1. These solutions were prepared from nitrate salt and
deionized water. Standard procedures were used to determine
the adsorption capacity of modified carbons under static condi-
tions. Adsorption experiments were conducted in duplicate at
30 °C and pH 5.
2.3.2. Adsorption Isotherms of Zn2+, Cd2+, and Ni2+ Ions.
Adsorption isotherms of Zn2+, Cd2+, and Ni2+ ions were obtained
at pH 5 and 30 °C. Note that preliminary results indicate that these
operating conditions (i.e., pH and temperature) have been
identified as optimal for obtaining the maximum removal of
these heavy metals. Therefore, adsorption isotherms at tested
conditions are used to determine the maximum adsorption
capacities of both raw and modified carbons. Metal solutions
were prepared from nitrate salts and deionized water. All the
adsorption experiments were conducted in duplicate at batch
conditions and the average results are reported. All chemicals
were of analytical grade.
2.3.3. Adsorption Experiments in Binary Solutions of Zn2+,
Cd2+, and Ni2+ Ions. Binary solutions of Zn2+
Cd2+, Zn2+
Ni2+,
and Ni2+
Cd2+ were used in multicomponent adsorption
experiments. As stated, these solutions were also prepared from
nitrate salts and deionized water. Batch experiments were
performed using initial metal concentrations in the range of 0.3

2 mmol L
1. In particular, a full factorial experimental design was
applied to identify the competitive effects of these metal ions
9357
ARTICLE
Table 3. Results of the Taguchi Experimental Design and
Analysis of Variance for Zn2+ Removal Using Modified
Commercial Carbons
sum of variance,
factor squares, SS σF
A: carbon type 26.56 13.28
B: acid treatment 379.04 189.52
C: concentration of calcium solution (vol %) 73.70 36.85
D: temperature of thermal treatment (°C) 177.33 88.66
onto the adsorption capacities of the adsorbents tested. Note that
this experimental design includes different binary solutions with
the same concentration of co-ions. Therefore, we consider that
this experimental design is proper to obtain a general overview of
the adsorbent performance for the removal of heavy metals under
competitive conditions. Standard procedures were also applied
to perform these adsorption experiments using an adsorbent
dosage of 2 g L
1 at 30 °C and pH 5.
2.3.4. Metal Quantification. For metal quantification, a Perkin

Elmer AAnalyst 100 atomic absorption spectrophotometer
equipped with an air
acetylene burner was used. The reprodu-
cibility of the experiments was generally within 5% of the average
results. The adsorption capacities of carbons (q) were calculated
by a mass balance
ðC0
Cf ÞV
q¼ ð5Þ
W
where C0 and Cf is the initial and final metal concentration
(mg L
1), V is the volume of metal solution used for adsorption
experiments (in liters), and W is the amount of carbon mass
(in grams).
3. RESULTS
3.1. Taguchi Experimental Design and Statistical Analysis
of the Carbon Modification. Overall, nine carbons were
obtained from the orthogonal experimental design. Table 2
shows the results of Zn2+ adsorption experiments using these
carbon samples. In particular, Taguchi orthogonal design indi-
cates that the optimal conditions needed to obtain a modified
carbon with improved adsorption capacity for Zn2+ removal are
those employed in experiment 3: a coconut shell carbon treated
with H3PO4, impregnated with a calcium solution (concen-
tration of 100 vol %) and heated at 400 °C for 3 h. Interesting
trends were also identified in our results. Specifically, the Zn2+
adsorption capacity was higher in the carbon samples treated
with H3PO4 (i.e., samples CC-3, BC-3, and LC-3), most likely
because of the formation of calcium phosphate on the carbon
surface (see characterization results given below).
Figure 2 shows the S/N response graphs for the modification
of commercial carbons using HES wastes, and Table 3 provides
the ANOVA. Statistical analysis shows that the most important
experimental design factors are the acid treatment and the
calcium concentration employed during the activation step.
Finally, based on these results, and considering both the adsor-
bent cost and its availability, it was possible to select the ideal
carbon sample for additional experiments. Thus, the modified
carbon obtained in experiment 6 (i.e., sample BC-3) was selected
as the case study for performing removal experiments in both
single and binary metal solutions.
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Industrial & Engineering Chemistry Research ARTICLE

Table 4. Elemental Composition and Chemical and Physical

Properties of Bituminous Carbon Modified with a Phosphoric
Acid and Calcium Solution Extracted from Egg Shell Wastes
(Sample BC-3; see Table 2)

Elemental Composition
element content (%)

carbon 75.56
hydrogen 1.53
nitrogen 1.75
sulfur 0.20
oxygen 18.60

Textural Parameters Figure 3. N2 adsorption isotherms at
196 °C of raw (clear squares)

property value and modified (black squares) bituminous carbons.

SBET 931 m2 g
1

Vtotal 0.522 cm3 g
1
Vmic 0.355 cm3 g
1
Dp 2.243 nm

Results of the ultimate analysis and the chemical and physical

properties of the selected modified-carbon (BC-3) and raw
commercial carbon (BC) are shown in Tables 4 and 1, respec-
tively. Figure 3 shows the nitrogen adsorption isotherms of BC
and BC-3 and, according to the International Union of Pure and
Applied Chemistry (IUPAC) clasification, they are a combina-
tion between Type I (characteristic of microporous materials)
and Type IV (mesoporous materials). In general, all the chemical
and physical properties of raw BC were not significantly affected
when it was treated with the calcium solution and phosphoric
acid. These results suggest that only the surface chemistry of BC
was affected after the treatment. On the other hand, two
interesting aspects can be analyzed from the results of ultimate
analysis. First, the differences in carbon percentage may be
related to the incorporation of inorganic elements on the surface
of BC, thus increasing the quantity of ashes in BC-3 (8.3%), in
comparison with BC (6.1%). Second, the oxygen content is also
higher in the modified carbon, because of the treatment with Figure 4. X-ray diffraction (XRD) patterns of (a) raw and (b) modified
H3PO4. According to the literature,36 some phosphorus
oxygen bituminous carbons.
compounds may be formed onto carbon surfaces using this acid
treatment. Figure 4 shows the diffraction patterns of BC and BC-3, 3.2. Adsorption Isotherms of Zn2+, Cd2+, and Ni2+ Ions.
and it is possible to observe a significant difference between Figure 5 shows the adsorption isotherms of Zn2+, Cd2+, and Ni2+
these samples. In addition to common reflections observed in the ions from aqueous solution at pH 5 and 30 °C, using both BC and
diffraction patterns of the two carbon samples corresponding to BC-3. These isotherms indicate that the maximum adsorption
quartz and mullite crystalline phases, peaks assigned to calcium capacities for Zn2+, Cd2+, and Ni2+ can be significantly enhanced
phosphate were identified in the diffraction pattern of sample after chemical modification of BC carbon using H3PO4 and
BC-3 (see Figure 4b). Therefore, our results indicate that the calcium solution extracted from HES waste. Specifically, the
carbon modification using HES and H3PO4 caused the formation maximum adsorption capacities for Zn2+, Cd2+, and Ni2+ ions
of surface moieties containing phosphorus and calcium. These are, respectively, 0.63, 0.61, and 1.0 mg g
1 for BC, and 10.48,
moieties are expected to increase the adsorption properties of 5.7, and 9.96 mg g
1 for BC-3; i.e., BC-3 loading capacities are an
modified carbons via surface complexation reactions. It is im- order of magnitude higher than those values observed for BC. It
portant to note that similar findings have been reported for other is interesting to remark that, although the adsorbent performance
commercial carbons impregnated with metal ions.37 For exam- for the removal of Cd2+ and Ni2+ was not considered in the
ple, Yang et al.37 reported the improvement of Cu2+ adsorption Taguchi experimental design, the optimal conditions identified
properties of activated carbon by loading of Fe3+ on carbon for the modification of BC also improved the adsorption proper-
surface. These authors suggested that the improvement of ties for these metallic ions.
adsorbent properties could be explained by complexation reac- For illustrative purposes, the adsorption capacities of BC-3
tions between heavy-metal ions and metal-modified carbon were compared with those reported in the literature for pow-
surface. dered egg shell (PES).38 In particular, Otun et al.38 reported a
9358 dx.doi.org/10.1021/ie2006627 |Ind. Eng. Chem. Res. 2011, 50, 9354–9362
Industrial & Engineering Chemistry Research ARTICLE

Figure 5. Adsorption isotherms of Zn2+, Ni2+, and Cd2+ ions on raw and modified bituminous carbons at 30 °C and pH 5.

Figure 6. Comparison of experimental and calculated adsorption capacities by raw and modified bituminous carbons using (a) the Langmuir model and
(b) the Freundlich model.

maximum adsorption capacity of 7 and 4 mg g
1 for Ni2+ and reuse of egg shell wastes is attractive from the viewpoint of the
Cd2+ ions, respectively, using PES. It is clear that the adsorption waste recycle and minimization of pollutants.
capacities of BC-3 are higher than those reported for raw PES and On the other hand, we have considered both the Langmuir and
BC. Therefore, the procedure proposed in this study for the Freundlich models for correlating the adsorption isotherms
modification of adsorption properties of commercial carbons is reported in Figure 5. Specifically, the Langmuir isotherm as-
an alternative strategy for developing new and effective adsor- sumes that adsorption occurs in a monolayer, where the actives
bents for the removal of heavy metals from water. Moreover, the sites are identical and energetically equivalent.39,40 This isotherm
9359 dx.doi.org/10.1021/ie2006627 |Ind. Eng. Chem. Res. 2011, 50, 9354–9362
Industrial & Engineering Chemistry Research ARTICLE

Table 5. Parameters of Langmuir and Freundlich Isotherm Results of data fitting for both isotherms are given in Figure 6
Models for Adsorption of Heavy Metals from Aqueous and Table 5. Overall, it is clear that our adsorption data are best
Solution described by the Langmuir model. Specifically, this isotherm
model showed a mean absolute percentage deviation (E) of 3.7%

Freundlich Model 14.9% and correlation coefficients (R2) of 0.85
0.99. Based on
these results, we have calculated the dimensionless separation
carbon sample metal ion Kf nF R2 Fobj E (%)
factor (RL) for the Langmuir isotherm. This separation factor is
BC Zn 2+
0.0171 1.4877 0.7004 0.2941 20.72 ( 8.55 given by
Cd2+ 0.0165 1.5211 0.9549 0.0712 7.99 ( 4.16
1
Ni2+ 0.0406 1.6574 0.7248 0.5055 20.08 ( 10.67 RL ¼ ð10Þ
BC-3 Zn 2+
0.4034 1.7742 0.9779 0.0370 5.24 ( 2.62
1 þ KC0
Cd2+ 0.1956 1.6148 0.9476 0.0895 8.37 ( 4.64 This separation factor indicates the type of the isotherm to be
Ni2+ 1.3597 1.7742 0.9519 0.0730 7.32 ( 4.64 either unfavorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1),
or irreversible (RL = 0). We have calculated the values of RL
Langmuir Model for the modified carbon BC-3 using different initial metal con-
carbon sample metal ion qmax K R2 Fobj E (%) centrations. Our results indicate that RL < 1 for all tested
conditions, confirming thereby the favorable adsorption of
BC Zn 2+
1.1649 0.0057 0.8537 0.1620 14.86 ( 7.67 heavy-metal ions onto the modified bituminous carbon BC-3.
Cd2+ 0.8535 0.0081 0.9950 0.0170 3.73 ( 2.23 3.3. Adsorption Experiments in Binary Solutions of Zn2+,
Ni2+ 1.4161 0.0116 0.9237 0.1950 11.42 ( 8.47 Cd2+, and Ni2+ Using the Modified Bituminous Carbon BC-3.
BC-3 Zn2+ 12.2449 0.0097 0.9511 0.2768 13.55 ( 8.66 The sorption studies of metal ions from solutions containing two
Cd2+ 7.6649 0.0099 0.9917 0.0279 4.83 ( 2.27 or more metallic species are useful to assess the degree of
Ni2+ 9.8083 0.0470 0.9621 0.0394 5.76 ( 2.70
interference between metal ions during the removal process.
When two or more metal ions are present in solution, they may
increase, decrease, or have no effect on the metal-ion adsorption
is given by capacity of the adsorbent.43,44 Thus, adsorption data from multi-
component solutions play an important role to design treatment
qm KCe
qe ¼ ð6Þ processes for wastewater. Experimental data for competitive
1 þ KCe adsorption in binary mixtures of Zn2+, Cd2+, and Ni2+ ions onto
where qe is the metal adsorption capacity (expressed in units of BC-3 are shown in Figure 7. In this figure, the metal adsorption
mg g
1) at equilibrium, Ce the concentration (expressed in units capacity of each co-ion is plotted as a function of the initial
of mg L
1) at equilibrium, qm the theoretical maximum adsorp- concentration of the binary solution. For comparison purposes,
tion capacity (expressed in units of mg g
1), and K represents the the monocomponent adsorption capacity of each metal is also
Langmuir equilibrium constant (expressed in units of L mg
1). reported. Note that the performance of raw BC in binary metal
The Freundlich model is an empirical expression used to solutions is not reported, because its adsorption capacities under
describe a heterogeneous system39,40 and is defined as competitive conditions are practically negligible.
To perform the experimental data analysis, the effect of co-ions
qe ¼ Kf Ce 1=nF ð7Þ in multicomponent adsorption using BC-3 is determined by the
1
(1/n) 1/n
1 ratio of adsorption capacities (Rq), which is defined as
where Kf (expressed in units of mg L g ) and nF are
parameters characteristic of the adsorbent-sorbate system. Data qi, mix
Rq, i ¼ ð11Þ
correlation of our experimental results was performed using a qi, 0
nonlinear regression approach,40
42 based on the minimization
of the following objective function: where qi,mix is the adsorption capacity for metal ion i in the
!2 presence of the other metal ion and qi,0 is the adsorption capacity
e
qe
qexp
ndat calc
∑
for the same metal when it is alone in the solution at the same
Fobj ¼ exp ð8Þ initial concentration of that set in the binary solution. According
i¼1 qe
i to the literature,45 if Rq,i > 1, the adsorption of metal i is promoted
where qexp
e and qexp
e are the experimental and predicted adsorption by the presence of other metal ions; if Rq,i = 1, there is no effect on
capacity and ndat is the overall number of experimental data, the adsorption capacity of metal i; and if Rq,i < 1, the adsorption of
respectively. In this study, the stochastic optimization method metal i is suppressed by other metal ions. Therefore, this analysis
Simulated Annealing41 was used for minimization of eq 10. The has been used to study the performance of BC-3 in the removal of
criterions used in this study to measure the fitting goodness of the Zn2+, Cd2+, and Ni2+ ions under competitive conditions. It is
adsorption isotherm models were the correlation coefficient (R2), convenient to remark that the adsorption capacities from Figure 7
the behavior of the relative residuals, the objective function value have been standardized and are reported on a molar basis for a
(Fobj), and the mean absolute percentage deviation (E) between direct comparison, because the analysis of adsorption behavior
calculated and experimental metal adsorption capacities, where may be misinterpreted when they are reported on a weight basis.
In general, our results indicate that there is an antagonistic
  effect of all co-ions in the adsorption process of all binary
100 ndat qexp calc 
e
qe 
systems. For all metallic ions, Rq.i is less than unity, indicating
E¼ ∑

ndat i ¼ 1  qe
exp 

ð9Þ that the simultaneous presence of other ions reduced the metal
i removal, because of competition effects during the adsorption
9360 dx.doi.org/10.1021/ie2006627 |Ind. Eng. Chem. Res. 2011, 50, 9354–9362
Industrial & Engineering Chemistry Research
Figure 7. Results for competitive adsorption in binary mixtures of Zn2+, Cd2+, and Ni2+ ions onto modified bituminous carbon BC-3 at 30 °C and pH 5.
process. The increase of co-ion concentration may enhance the
interaction between the metal ions in the aqueous phase and the
adsorbent and, as a consequence, the competitive adsorption
effect is dependent on the co-ion concentration; its magnitude is
also different for the different heavy metals (see Figure 7). In
particular, the adsorption of Cd2+ ions is not affected significantly
by co-ion competition of Zn2+ and Ni2+ ions, especially at high
Cd2+ initial concentrations. It is interesting to observe that Ni2+
adsorption using BC-3 decreases with Zn2+ concentration, while
Zn2+ uptake decreased significantly when Ni2+ ions are present.
Overall, the metal uptake reduction ranged from 0.1% to 77% for
the Ni2+ ion, from 3% to 57% for the Zn2+ ion, and from 0.1% to
43% for the Cd2+ ion in all experiments performed.
4. CONCLUSIONS
Our study shows that the adsorption properties of commercial
carbons can be significantly improved for the removal of heavy
metals, using, as an activation agent, a calcium solution extracted
from egg shell in combination with an acid treatment using
H3PO4. It appears that the improvement of adsorption proper-
ties of these modified carbons relies on the formation of calcium
phosphate on the adsorbent surface, which may favor the
presence of complexation reactions that increase the removal
of heavy-metal ions. Generally, the adsorption capacities of
modified carbons can be an order of magnitude higher than
those obtained using raw commercial adsorbents. On the other
hand, the effect of co-ions in multicomponent adsorption of
heavy metals using a bituminous carbon modified with egg shell
wastes has been studied. Results indicate that the adsorption of
Cd2+, Zn2+, and Ni2+ ions is affected by the co-ion competition,
9361
ARTICLE
especially at high metal concentrations. Overall, the metal uptake
reduction may range from 0.1% to 77%, depending on the binary
system under study.
In summary, this study provides new insights to develop
alternative adsorbents with selective properties for the removal
of metallic ions from wastewaters using low-cost reagents such as
egg shell wastes. Further studies will be focused on the applica-
tion of these calcium-modified adsorbents using packed-bed
columns for the treatment of wastewater polluted by heavy-
metal ions.
’ AUTHOR INFORMATION
Corresponding Author
*Tel.: 52 449 9105002, ext. 127. E-mail: petriciolet@hotmail.com.
’ ACKNOWLEDGMENT
Authors acknowledge the financial support provided by
CONACYT, DGEST, Instituto Tecnol
ogico de Aguascalientes
(M
exico), and MICINN-Spain (CTM2008-06869-C02-01/
PPQ).
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